CN110256698A - A kind of cellulose solvent and its preparation method and application - Google Patents
A kind of cellulose solvent and its preparation method and application Download PDFInfo
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- CN110256698A CN110256698A CN201910460353.2A CN201910460353A CN110256698A CN 110256698 A CN110256698 A CN 110256698A CN 201910460353 A CN201910460353 A CN 201910460353A CN 110256698 A CN110256698 A CN 110256698A
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Abstract
The present invention relates to a kind of cellulose solvents and its preparation method and application.The preparation method of the cellulose solvent is placed in three-necked flask the following steps are included: chemical structure is mixed with the organic base of miscellaneous two ring with organic solvent, logical nitrogen, acid reagent is added dropwise into reaction system under magnetic stirring, temperature in entire reaction process is set to be maintained at 30 DEG C hereinafter, obtaining transparent mixture；Mixture is continued to stirring at room temperature reacts it sufficiently, and non-imidazole class ionic liquid is precipitated from organic phase, after separation, obtains non-imidazole class ionic liquid；Under inert gas protection by non-imidazole class ionic liquid, it heats, obtains dry cellulose solvent.The preparation and use that the present invention passes through non-imidazole ionic liquid cellulose solvent, improve solute effect of the cellulose in the non-imidazole ionic liquid of relative low price, the maxima solubility for especially increasing cellulose shortens the cellulose dissolution time, significantly reduces the degradation rate of cellulose.
Description
Technical field
The invention belongs to cellulose solvent technical fields, more particularly to a kind of cellulose solvent and preparation method thereof and use
On the way.
Background technique
Cellulose is the most abundant biorenewable of nature and biodegradable resource, is main group of plant cell wall
/ mono-, account for 50% or more of plant kingdom's carbon content.Using cellulose and its esters or the film of ether derivative exploitation, silk, coagulate
The biomass-based material such as glue, microballoon, in weaving, plastics, medicine, electrician, architectural design, Scientific Research Equipments, daily-use chemical industry and food
The fields such as additive have broad application prospects.And the preparation and application of cellulose based product and the close phase of its solubility property
It closes.
Cellulose is as D- glucopyranosyl by linear macromolecule polysaccharide made of β-Isosorbide-5-Nitrae glucosides key connection, wherein
Containing a large amount of alcoholic OH groups, multiple intermolecular and intramolecular hydrogen bond forms complicated cellulose hydrogen bond network structure,
Most of hydroxyl is weakened to the affinity interaction of water, makes cellulose that there is good chemistry and mechanical stability, it is difficult to be dissolved in water
In most of common organic solvents.Currently, the industrialization dicyandiamide solution of dissolution cellulose is NaOH/CS2Dicyandiamide solution (viscose glue
Method) and NMMO (N-methylmorpholine-N- oxide) dicyandiamide solution (lyocell method).Viscose process is production glassine paper and viscose rayon
Traditional handicraft, in occupation of main status in regenerated cellulosics field, but process is tedious, process for this method production process
Length generates a large amount of toxic gases and waste water, causes serious pollution to environment.Lyocell method is produced using green solvent NMMO
The technique of regenerated cellulose, preparation process is environmental-friendly, but that there are solvents is expensive, and recycling is difficult, and amine oxide solvent
There is the problems such as potential explosive during cellulose regenerated, is unfavorable for sustainable development.
In recent years, more researchers are by the shift of the work focus to the development field of novel green solvent system.Example
Such as, application No. is the Chinese patent applications of CN201610255183.0 to disclose one kind quickly directly dissolution at -10 DEG C~5 DEG C
The solvent of cellulose is made of the aqueous solution of sodium hydroxide and thiocarbamide.Application No. is the Chinese patents of CN201710414026.4
Shen Qing Publication is with molecular weight for 7.0 × 104~3.0 × 105Native cellulose be raw material, be scattered in alkyl phosphonium hydroxide
In aqueous ammonium, freeze dispersion liquid at -10 DEG C~-30 DEG C, homogeneous and transparent cellulose solution is obtained after thawing at room temperature.
Glyoxaline ion liquid is one of novel green non-derivative dicyandiamide solution of rising in recent years, compared with other solvents, imidazoles
Class ionic liquid has many advantages, such as fixedness, chemical and thermal stability, incombustibility, lower vapour pressure.2002,
Rogers etc. reports alkyl imidazole ionic liquid 1- butyl -3- methylimidazolium chloride villaumite ([C for the first time4Mim] Cl) it can make
Physical dissolution and regeneration are carried out to it for cellulose solvent, open the research field of a kind of novel cellulose solvent.
However existing cellulose dissolution system has the disadvantage in that sodium hydroxide/thiocarbamide equal solvent system uses alkalinity
Solution, it is difficult to meet the requirement of environmental protection, and (- 12 DEG C) of low temperature operations are needed, energy consumption is higher, is unfavorable for industrialization promotion；Using alkane
For base ammonium hydroxide aqueous solution system although a large amount of celluloses can be dissolved, dissolution conditions are harsh, the requirement to cellulosic material compared with
It is high, it is difficult to realize industrial applications；Glyoxaline ion liquid dissolution system viscosity is big, synthesis condition is harsh, solution temperature is high, meets
Water sensitive, and the ionic liquid of superior solubility is at high price, and the ion liquid dissolving time of relative low price is long, it is fine
Dimension element can occur seriously to degrade, and hinder large-scale industrial production.
Therefore, there is still a need for developing, a kind of synthetic method is simple, cheap, environmentally protective, superior solubility height
Dicyandiamide solution is imitated, this is very necessary to the higher value application of cellulose resource.
Summary of the invention
In order to solve the above problems existing in the present technology, the present invention provides a kind of cellulose solvents and preparation method thereof
And purposes, the dicyandiamide solution synthesis condition is mild, method is simple, cheap, performance is stable, environmentally protective, cellulose dissolution
Degree is high, Yi Shixian industrialization.
A kind of preparation method for cellulose solvent that embodiment according to the present invention proposes, comprising the following steps:
(1) chemical structure is mixed with the organic base of miscellaneous two ring with organic solvent and is placed in three-necked flask, lead to nitrogen,
Acid reagent is added dropwise under magnetic agitation into reaction system, temperature in entire reaction process is made to be maintained at 30 DEG C hereinafter, obtaining
Bright mixture；
(2) mixture that step (1) obtains is continued stirring at room temperature reacts it sufficiently, non-imidazole class ion
Liquid is precipitated from organic phase, after separation, obtains non-imidazole class ionic liquid；
(3) under inert gas protection, heating obtains dry fibre to the non-imidazole class ionic liquid for obtaining step (2)
Tie up plain solvent.
Further, wherein in step (1), the organic base is selected from 1,5- diazabicyclo [4,3,0] nonyl- 5- alkene
(DBN), 11 carbon -7- alkene (DBU) of 1,8- diazabicylo [5.4.0] or 1,4- diazabicylo [2.2.2] octane (TEDA)
One of, 11 carbon -7- alkene (DBU) of more preferably 1,8- diazabicylo [5.4.0], this is because utilizing DBU synthesis
Ionic liquid is higher to the solubility of cellulose.
Further, wherein in step (1), the organic solvent is selected from one of n-hexane or ether.
Further, wherein in step (1), the acid reagent is selected from acrylic acid (CH2=CHCOOH), methoxyl group second
Acid (CH3OCH2COOH), ethoxyacetic acid (CH3CH2OCH2COOH), thioglycolic acid (HSCH2COOH), benzoic acid ((C6H5)
COOH), amion acetic acid (H2NCH2COOH), glycolic (HOCH2COOH), lactic acid (CH3CHOHCOOH), niacin ((C5H4N)
COOH), isonicotinic acid ((C5H4N) COOH), 2- chlorine apellagrin ((C5H3N) ClCOOH), gluconic acid (HOCH2(CHOH)4COOH)、2-
Chloropropionic acid (CH3CHClCOOH), pyruvic acid (CH3COCOOH), 3- mercaptopropionic acid (HSCH2CH2COOH), septichen
((C6H4) OHCOOH), cinnamic acid ((C6H5) CH=CHCOOH), α-methacrylic acid (CH2=CCH3) or undecenoic acid COOH
(CH2=CH (CH2)8One of COOH).
Further, wherein the acid reagent is selected from acrylic acid (CH when the organic base is selected from DBU2=
CHCOOH), methoxyacetic acid (CH3OCH2COOH), ethoxyacetic acid (CH3CH2OCH2COOH), thioglycolic acid
(HSCH2COOH), benzoic acid ((C6H5) COOH), amion acetic acid (H2NCH2COOH), glycolic (HOCH2COOH), lactic acid
(CH3CHOHCOOH), niacin ((C5H4N) COOH), isonicotinic acid ((C5H4N) COOH), 2- chlorine apellagrin ((C5H3N) ClCOOH), Portugal
Grape saccharic acid (HOCH2(CHOH)4COOH), 2- chloropropionic acid (CH3CHClCOOH), pyruvic acid (CH3COCOOH), 3- mercaptopropionic acid
(HSCH2CH2COOH), septichen ((C6H4) OHCOOH), cinnamic acid ((C6H5) CH=CHCOOH), Alpha-Methyl propylene
Acid (CH2=CCH3COOH), undecenoic acid (CH2=CH (CH2)8COOH), formic acid (HCOOH), acetic acid (CH3COOH), propionic acid
(CH3CH2COOH), n-butyric acie (CH3(CH2)2COOH), isobutyric acid (CH3(CH2)2COOH), n-caproic acid (CH3(CH2)4COOH), nonyl
Acid (CH3(CH2)7) or lauric acid (CH COOH3(CH2)10One of COOH).
Further, wherein in step (1), the acid reagent is preferably acrylic acid (CH2=CHCOOH), methoxyl group second
Acid (CH3OCH2COOH), ethoxyacetic acid (CH3CH2OCH2COOH), thioglycolic acid (HSCH2) or glycolic COOH
(HOCH2One of COOH).
Further, wherein in step (1), the volume ratio of the organic base and organic solvent is 1:2~1:4, organic base
Molar ratio with acid reagent is 1:0.9~1:1.
Further, wherein in step (1), the magnetic agitation rotating speed is 200rpm~400rpm, the acid reagent
Rate of addition be 30 drops/min~70 drops/min, the temperature of the reaction system is 25 DEG C~30 DEG C.
Further, wherein in step (2), the speed of agitator be 200rpm~400rpm, mixing time be 8h~
16h。
Further, wherein in step (3), the inert gas is argon gas, nitrogen, preferably argon gas.
Further, wherein in step (3), the heating temperature is 70 DEG C~90 DEG C, and heating time is 1h~3h.
A kind of cellulose solvent that embodiment according to the present invention proposes, the cellulose solvent is by any of the above-described
Method preparation.
The cellulose solvent system proposed according to one embodiment of present invention is preparing the use in cellophane
On the way.
Further, wherein the purposes the following steps are included:
1) by cellulosic pulp board impurity removing, crushing, powdered or cotton shape cellulosic material is formed；
2) cellulosic material for obtaining step 1) is added in the cellulose solvent, dissolves by heating under magnetic agitation,
Obtain transparent homogeneous cellulose solution；
3) after the solution left standstill deaeration that step 2) obtains, glass plate is placed in baking oven and puts by the film on smooth glass plate
It sets, keeps film surface smooth；
4) glass plate is put into regenerated solvent, is solidified and is regenerated at room temperature, gained film regenerated solvent is clear
4~6 times are washed to no ionic liquid；
5) film is placed at room temperature for 24 hours~48h to dry, obtains RCF regenerated cellulose film.
Further, wherein in step 1), the cellulose slurry board raw material is the cellulose that the degree of polymerization is 100~1200,
Including the higher raw material of the content of cellulose such as cotton linter, poplar pulpboard, cotton starch plate, microcrystalline cellulose or alpha-cellulose.
Further, wherein in step 2), the cellulose solvent system is 1,8- diazabicylo [5.4.0] 11
Carbon -7- alkene acrylates ([DBUH] [CH2=CHCOO]), 11 carbon -7- alkene methoxyl group second of 1,8- diazabicylo [5.4.0]
Hydrochlorate ([DBUH] [CH3OCH2COO]), 11 carbon -7- alkene ethoxyacetic acid salt ([DBUH] of 1,8- diazabicylo [5.4.0]
[CH3CH2OCH2COO]), 11 carbon -7- alkene thioglycolic hydrochlorate ([DBUH] of 1,8- diazabicylo [5.4.0]
[HSCH2COO]), 11 carbon -7- alkene glycollate ([DBUH] [HOCH of 1,8- diazabicylo [5.4.0]2COO]) etc. in extremely
Few one kind, when the cellulose solvent is two kinds of mixing, mixing quality ratio is 1:9~5:5.
Further, wherein in step 2), the mass percent concentration of the homogeneous cellulose solution is 2%~12%,
Preferably 4~6%；The solution temperature of the cellulosic material be 60 DEG C~90 DEG C, magnetic agitation rotating speed be 100rpm~
300rpm, the time that dissolution accounts for the cellulosic material of the cellulose solvent system weight 5% is 10min to 150min.
Further, wherein in step 3), the coating thickness is 0.4mm~0.6mm, and oven temperature is 70 DEG C~105
DEG C, preferably 90 DEG C.
Further, wherein in step 4), the regenerated solvent in deionized water, dehydrated alcohol or acetone one
Kind, the scavenging period of the regenerated solvent is 30min~45min.
Further, wherein in step 4), the regenerated solvent is preferably deionized water, this is because again with deionized water
Raw film strength is higher.
The present invention at least has the advantages that
It is opposite in price to improve cellulose by the preparation and use of non-imidazole ionic liquid cellulose solvent by the present invention
Solute effect in cheap non-imidazole ionic liquid, especially increases the maxima solubility of cellulose, it is molten to shorten cellulose
The time is solved, the degradation rate of cellulose is significantly reduced, can be used for preparing fibrous composite, expand the kind of non-imidazole ionic liquid
Class and use scope；In addition, preparation process of the invention is economical and practical, preparation process is simple, low in cost, is not necessarily to special installation
And harsh conditions, it is easy to accomplish industrialized production；Operating process does not use toxic, harmful reagent, and process is environmentally friendly, recyclable, mentions
The high economic feasibility of novel dissolvent system, has stronger application value.In addition, dicyandiamide solution synthesis condition of the invention
Mildly, method is simple, cheap, performance is stable, environmentally protective, cellulose dissolution degree is high, Yi Shixian industrialization.
Detailed description of the invention
Fig. 1 is the structural formula of cellulose solvent described in 1-6 of the embodiment of the present invention；
Fig. 2 is the structural formula of cellulose solvent described in the embodiment of the present invention 7；
Fig. 3 is the structural formula of cellulose solvent described in the embodiment of the present invention 8.
Specific embodiment
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
For ionic liquid 100% by anion and cation composition, the type of the ability and ion that dissolve cellulose is close
It is related.In course of dissolution, the hydrogen atom on the anion and cellulose hydroxyl group of ionic liquid forms hydrogen bond, cation and fiber
Oxygen atom on plain hydroxyl forms hydrogen bond, to break the hydrogen bond of cellulose itself, so that cellulosic molecule aggregation dissociates
It is distributed in solvent and dissolves.
The general structure of the non-imidazole class ionic liquid of DBU- base is as shown in Figure 1.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.Unless stated otherwise, material used in the following embodiment, reagent and instrument are commercially available product.
One, cellulose dissolution
Embodiment 1
It takes 15.224g organic base DBU and 45mL n-hexane in three-necked flask, leads to nitrogen, in the magnetic agitation of 200rpm
Under, 7.206g acrylic acid is slowly added dropwise with 30 drops/min speed into reaction system, temperature of reaction system control during dropwise addition
System is at 25 DEG C, after acrylic acid is added completely into, continues to stir 8h with 200rpm at room temperature, non-imidazole class ionic liquid is from n-hexane
It is precipitated, after separation, under protection of argon gas, 80 DEG C of heating 2h are finally obtained dry the non-imidazole class ionic liquid of obtained high-purity
Dry cellulose solvent [DBUH] [CH2=CHCOO] (its structural formula is shown in Fig. 1).It weighs microcrystalline cellulose and above-mentioned cellulose is added
In solvent, in 80 DEG C, 200rpm continues to stir, until can not dissolve, obtains the homogeneous phase solution dissolved with microcrystalline cellulose.Through dividing
Analysis can obtain, and the maxima solubility of microcrystalline cellulose is 23.5%, and the solubility is molten divided by cellulose by microcrystalline cellulose quality
Agent [DBUH] [CH2=CHCOO] quality obtain, wherein measurement dissolution account for cellulose solvent quality 5% cellulose time
For 18min.
Embodiment 2
It takes 13.702g organic base DBU and 50mL n-hexane in three-necked flask, leads to nitrogen, under 400rpm magnetic agitation,
9.008g methoxyacetic acid is slowly added dropwise with 40 drops/min speed into reaction system, temperature of reaction system control during dropwise addition
System is at 30 DEG C, after methoxyacetic acid is added completely into, continues to stir 10h with 400rpm at room temperature, non-imidazole class ionic liquid is from just
Be precipitated in hexane, after separation, the non-imidazole class ionic liquid of obtained high-purity under protection of argon gas, 80 DEG C of heating 2h, finally
Obtain dry cellulose solvent [DBUH] [CH3OCH2COO] (its structural formula is shown in Fig. 1).It weighs microcrystalline cellulose and above-mentioned fibre is added
It ties up in plain solvent, in 80 DEG C, 200rpm continues to stir, until can not dissolve, obtains the homogeneous phase solution dissolved with microcrystalline cellulose.
It can be obtained through analysis, the maxima solubility of microcrystalline cellulose is 22.8%, and the solubility is by microcrystalline cellulose quality divided by fiber
Plain solvent [DBUH] [CH3OCH2COO] quality obtain, wherein measurement dissolution account for cellulose solvent quality 5% cellulose when
Between be 20min.
Embodiment 3
It takes 15.224g organic base DBU and 50mL ether in three-necked flask, leads to nitrogen, under 300rpm magnetic agitation, to
9.212g thioglycolic acid is slowly added dropwise with 40 drops/min speed in reaction system, temperature of reaction system controls during dropwise addition
At 28 DEG C, after thioglycolic acid is added completely into, continue to stir 11h with 300rpm at room temperature, non-imidazole class ionic liquid is from ether
Middle precipitation, after separation, under nitrogen protection, 80 DEG C of heating 2h are finally obtained the non-imidazole class ionic liquid of obtained high-purity
Dry cellulose solvent [DBUH] [HSCH2COO] (its structural formula is shown in Fig. 1).It weighs microcrystalline cellulose and above-mentioned cellulose is added
In solvent, in 80 DEG C, 200rpm continues to stir, until can not dissolve, obtains the homogeneous phase solution dissolved with microcrystalline cellulose.Through dividing
Analysis can obtain, and the maxima solubility of microcrystalline cellulose is 20%, and the solubility is by microcrystalline cellulose quality divided by cellulose solvent
[DBUH][HSCH2COO] quality obtain, wherein time of cellulose that measurement dissolution accounts for cellulose solvent quality 5% is
36min。
Embodiment 4
It takes 14.463g organic base DBU and 60mL ether in three-necked flask, leads to nitrogen, under 400rpm magnetic agitation, to
6.005g glycolic is slowly added dropwise with 40 drops/min speed in reaction system, temperature of reaction system control is 25 during dropwise addition
DEG C, after glycolic is added completely into, continue to stir 12h with 400rpm at room temperature, non-imidazole class ionic liquid is precipitated from ether, passes through
After separation, under protection of argon gas, 70 DEG C of heating 3h finally obtain dry fiber to the non-imidazole class ionic liquid of obtained high-purity
Plain solvent [DBUH] [HOCH2COO] (its structural formula is shown in Fig. 1).It weighs microcrystalline cellulose to be added in above-mentioned cellulose solvent, in 80
DEG C, 200rpm continues to stir, until can not dissolve, obtains the homogeneous phase solution dissolved with microcrystalline cellulose.It can be obtained through analysis, crystallite
The maxima solubility of cellulose is 10.2%, and the solubility is by microcrystalline cellulose quality divided by cellulose solvent [DBUH]
[HOCH2COO] quality obtain, wherein measurement dissolution account for cellulose solvent quality 5% cellulose time be 75min.
Embodiment 5
It takes 15.224g organic base DBU and 50mL ether in three-necked flask, leads to nitrogen, under 400rpm magnetic agitation, to
10.41g ethoxyacetic acid is slowly added dropwise with 30 drops/min speed in reaction system, temperature of reaction system controls during dropwise addition
At 30 DEG C, after ethoxyacetic acid is added completely into, continue to stir 14h with 400rpm at room temperature, non-imidazole class ionic liquid is from ether
Middle precipitation, after separation, under protection of argon gas, 70 DEG C of heating 3h are finally obtained the non-imidazole class ionic liquid of obtained high-purity
Dry cellulose solvent [DBUH] [CH3CH2OCH2COO] (its structural formula is shown in Fig. 1).It weighs microcrystalline cellulose and above-mentioned fibre is added
It ties up in plain solvent, in 80 DEG C, 200rpm continues to stir, until can not dissolve, obtains the homogeneous phase solution dissolved with microcrystalline cellulose.
It can be obtained through analysis, the maxima solubility of microcrystalline cellulose is 21.4%, and the solubility is by microcrystalline cellulose quality divided by fiber
Plain solvent [DBUH] [CH3CH2OCH2COO] quality obtain, wherein measurement dissolution accounts for the cellulose of cellulose solvent quality 5%
Time be 24min.
Embodiment 6
Weigh [the DBUH] [CH prepared in 10g above-described embodiment 53CH2OCH2COO] with prepared in 10g above-described embodiment 1
[DBUH] [CH2=CHCOO], after mixing, stirred to transparent and homogeneous liquid with 200rpm to be mixed at 80 DEG C
Cellulose solvent weighs microcrystalline cellulose and is added in above-mentioned cellulose mixture solvent, and in 80 DEG C, 200rpm continues to stir, until
It can not dissolve, obtain the homogeneous phase solution dissolved with microcrystalline cellulose.It can be obtained through analysis, the maxima solubility of microcrystalline cellulose is
26.3%, the solubility is obtained by microcrystalline cellulose quality divided by the quality of the cellulose mixture solvent, wherein measuring molten
The cellulose time that solution accounts for non-imidazole ionic liquid quality 5% is 14min.
Embodiment 7
It takes 12.418g organic base DBN and 30mL n-hexane in three-necked flask, leads to nitrogen, under 200rpm magnetic agitation,
7.206g acrylic acid is slowly added dropwise with 38 drops/min speed into reaction system, temperature of reaction system control exists during dropwise addition
25 DEG C, after acrylic acid is added completely into, continue to stir 8h with 200rpm at room temperature, non-imidazole class ionic liquid is analysed from n-hexane
Out, after separation, under protection of argon gas, 80 DEG C of heating 2h finally obtain drying to the non-imidazole class ionic liquid of the high-purity obtained
Cellulose solvent [DBNH] [CH2=CHCOO] (its structural formula is shown in Fig. 2).It is molten to weigh the above-mentioned cellulose of microcrystalline cellulose addition
In agent, in 80 DEG C, 200rpm continues to stir, until can not dissolve, obtains the homogeneous phase solution dissolved with microcrystalline cellulose.Through analyzing
It can obtain, the maxima solubility of microcrystalline cellulose is 20.7%, and the solubility is by microcrystalline cellulose quality divided by cellulose solvent
[DBNH][CH2=CHCOO] quality obtain, wherein time of cellulose that measurement dissolution accounts for cellulose solvent quality 5% is
20min。
Embodiment 8
It takes 11.217g organic base TEDA and 30mL ether in three-necked flask, leads to nitrogen, under 400rpm magnetic agitation,
7.206g acrylic acid is slowly added dropwise with 35 drops/min speed into reaction system, temperature of reaction system control exists during dropwise addition
28 DEG C, after acrylic acid is added completely into, continuing to stir 8h with 400rpm at room temperature, non-imidazole class ionic liquid is precipitated from ether,
After separation, under protection of argon gas, 90 DEG C of heating 1h finally obtain dry fibre to the non-imidazole class ionic liquid of the high-purity obtained
Tie up element solvent [TEDAH] [CH2=CHCOO] (its structural formula is shown in Fig. 3).It weighs microcrystalline cellulose and above-mentioned cellulose solvent is added
In, in 80 DEG C, 200rpm continues to stir, until can not dissolve, obtains the homogeneous phase solution dissolved with microcrystalline cellulose.It can through analysis
, the maxima solubility of microcrystalline cellulose is 8.7%, and the solubility is by microcrystalline cellulose quality divided by cellulose solvent
[TEDAH][CH2=CHCOO] quality obtain, wherein time of cellulose that measurement dissolution accounts for cellulose solvent quality 5% is
92min。
Two, film preparation
EXPERIMENTAL EXAMPLE 1
Weigh non-imidazole ionic liquid [the DBUH] [CH prepared in 20g above-described embodiment 12=CHCOO] in beaker, in advance
Heat is to 80 DEG C.0.8g cotton linter is added under 100rpm magnetic agitation, 80 DEG C of heating 1.5h to cotton linter are completely dissolved, and are stood and are protected
Warm 1h is defoamed to complete.Then, using the solution after defoaming on smooth glass plate film, with a thickness of 0.50mm, by glass plate
It is placed in 80 DEG C of baking ovens and places 10s, keep film surface smooth.Then, the glass plate for coating film is put into deionized water at room temperature
It is solidified and is regenerated in bath, after gained film cleans 30min to no ionic liquid with deionized water, be placed in and dry at room temperature, obtain
RCF regenerated cellulose film.Extension test process are as follows: the RCF regenerated cellulose film is cut into fixed dimension, is placed in Zwick/
In two fixtures of Roell tensilometer, so that the RCF regenerated cellulose film longitudinal axis is coincided with upper and lower clamp central line, start stretching
Instrument starts to test, until film fracture；Drawn test shows that film-strength up to 124MPa, dissolves film strength than conventional
It is high.Be conducive to widen the application field of film in this way and increase the timeliness etc. of application.
EXPERIMENTAL EXAMPLE 2
Weigh non-imidazole ionic liquid [the DBUH] [CH prepared in 20g above-described embodiment 23OCH2COO] in beaker, in advance
Heat is to 80 DEG C.1.2g microcrystalline cellulose is added under 100rpm magnetic agitation, 90 DEG C of heating 2h to microcrystalline cellulose are completely dissolved,
Heat preservation 1h is stood to complete defoaming.Then, using the solution after defoaming, film will with a thickness of 0.56mm on smooth glass plate
Glass plate is placed in 100 DEG C of baking ovens and places 10s, keeps film surface smooth.Then, the glass plate for coating film is put into nothing at room temperature
It is solidified and is regenerated in water-ethanol bath, gained film is placed in and is dried in the air at room temperature with after washes of absolute alcohol 45min to no ionic liquid
It is dry, obtain RCF regenerated cellulose film.Extension test process are as follows: the RCF regenerated cellulose film is cut into fixed dimension, is placed in
In two fixtures of Zwick/Roell tensilometer, so that the RCF regenerated cellulose film longitudinal axis is coincided with upper and lower clamp central line, open
Dynamic tensilometer starts to test, until film fracture；Drawn test shows that film-strength up to 108MPa, is dissolved into than conventional
Film-strength is high.Be conducive to widen the application field of film in this way and increase the timeliness etc. of application.
EXPERIMENTAL EXAMPLE 3
[the DBUH] [CH prepared in 10g above-described embodiment 53CH2OCH2COO] with prepared in 10g above-described embodiment 1
[DBUH][CH2=CHCOO] in beaker after mixing, stirring is to transparent and homogeneous liquid at 80 DEG C.In 100rpm magnetic force
It is added with stirring 0.8g cotton linter, 90 DEG C of heating 1h to cotton linter are completely dissolved, and stand heat preservation 1h to complete defoaming.Then, it adopts
With the solution after defoaming, glass plate is placed in 90 DEG C of baking ovens with a thickness of 0.58mm and places 10s by film on smooth glass plate,
Keep film surface smooth.Then, the glass plate for coating film is put at room temperature in deionization water-bath, is solidified and is regenerated, institute
After film cleans 35min to no ionic liquid with deionized water, be placed in and dry at room temperature, obtain RCF regenerated cellulose film.It stretches and surveys
Examination process are as follows: the RCF regenerated cellulose film is cut into fixed dimension, is placed in two fixtures of Zwick/Roell tensilometer, makes
The RCF regenerated cellulose film longitudinal axis coincides with upper and lower clamp central line, starts tensilometer and starts to test, until film is fractured into
Only；Drawn test shows that up to 139MPa, it is high to dissolve film strength than routine for film-strength.Be conducive to widen answering for film in this way
With field and increase the timeliness etc. applied.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention.Any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, according to the technical essence of the invention
Any simple modification, equivalent change and modification to the above embodiments, all of which are still within the scope of the technical scheme of the invention.
Claims (17)
1. a kind of preparation method of cellulose solvent, which comprises the following steps:
(1) chemical structure is mixed with the organic base of miscellaneous two ring with organic solvent and is placed in three-necked flask, lead to nitrogen, in magnetic force
Acid reagent is added dropwise under stirring into reaction system, temperature in entire reaction process is made to be maintained at 30 DEG C hereinafter, obtaining transparent
Mixture；
(2) mixture that step (1) obtains is continued stirring at room temperature reacts it sufficiently, non-imidazole class ionic liquid
It is precipitated from organic phase, after separation, obtains non-imidazole class ionic liquid；
(3) under inert gas protection, heating obtains dry cellulose to the non-imidazole class ionic liquid for obtaining step (2)
Solvent.
2. preparation method as described in claim 1, which is characterized in that in step (1), the organic base is selected from 1,5- phenodiazine
Miscellaneous bicyclic [4,3,0] nonyl- 5- alkene, 11 carbon -7- alkene of 1,8- diazabicylo [5.4.0] or 1,4- diazabicylo [2.2.2]
One of octane, the organic solvent are selected from one of n-hexane or ether.
3. preparation method as claimed in claim 2, which is characterized in that in step (1), the acid reagent is selected from propylene
Acid, methoxyacetic acid, ethoxyacetic acid, thioglycolic acid, benzoic acid, amion acetic acid, glycolic, lactic acid, niacin, isonicotinic acid,
2- chlorine apellagrin, gluconic acid, 2- chloropropionic acid, pyruvic acid, 3- mercaptopropionic acid, septichen, cinnamic acid, Alpha-Methyl propylene
One of acid or undecenoic acid.
4. preparation method as claimed in claim 3, which is characterized in that when the organic base is selected from 1,8- diazabicylo
When [5.4.0] 11 carbon -7- alkene, the acid reagent be selected from acrylic acid, methoxyacetic acid, ethoxyacetic acid, thioglycolic acid,
Benzoic acid, amion acetic acid, glycolic, lactic acid, niacin, isonicotinic acid, 2- chlorine apellagrin, gluconic acid, 2- chloropropionic acid, pyruvic acid, 3-
It is mercaptopropionic acid, septichen, cinnamic acid, α-methacrylic acid, undecenoic acid, formic acid, acetic acid, propionic acid, n-butyric acie, different
One of butyric acid, n-caproic acid, n-nonanoic acid or lauric acid.
5. preparation method as claimed in claim 4, which is characterized in that in step (1), the acid reagent is acrylic acid, first
One of ethoxyacetic acid, ethoxyacetic acid, thioglycolic acid or glycolic.
6. preparation method as claimed in claim 5, which is characterized in that in step (1), the body of the organic base and organic solvent
Ratio is accumulated as 1:2~1:4, the molar ratio of the organic base and acid reagent is 1:0.9~1:1；The magnetic agitation rotating speed is
200rpm~400rpm, the rate of addition of the acid reagent are 30 drops/min~70 drops/min, the temperature of the reaction system
It is 25 DEG C~30 DEG C.
7. preparation method as described in claim 1, which is characterized in that in step (2), the speed of agitator be 200rpm~
400rpm, mixing time are 8h~16h.
8. preparation method as described in claim 1, which is characterized in that in step (3), the inert gas is argon gas or nitrogen
Gas；The heating temperature is 70 DEG C~90 DEG C, and heating time is 1h~3h.
9. a kind of cellulose solvent, which is characterized in that the cellulose solvent is the method system by any one of claim 1-8
Standby.
10. a kind of cellulose solvent as claimed in claim 9 is in the purposes being used to prepare in cellophane.
11. purposes as claimed in claim 10, which is characterized in that the purposes the following steps are included:
1) by cellulosic pulp board impurity removing, crushing, powdered or cotton shape cellulosic material is formed；
2) cellulosic material for obtaining step 1) is added in the cellulose solvent, dissolves by heating, obtains under magnetic agitation
Transparent homogeneous cellulose solution；
3) after the solution left standstill deaeration that step 2) obtains, glass plate is placed in baking oven and places, makes by the film on smooth glass plate
Film surface is smooth；
4) glass plate being put into regenerated solvent, is solidified and is regenerated at room temperature, gained film cleans 4 with regenerated solvent~
6 times to no ionic liquid；
5) film is placed at room temperature for 24 hours~48h to dry, obtains RCF regenerated cellulose film.
12. purposes as claimed in claim 11, which is characterized in that in step 1), the cellulose slurry board raw material is the degree of polymerization
For 100~1200 cellulose, including cotton linter, poplar pulpboard, cotton starch plate, microcrystalline cellulose or alpha-cellulose.
13. purposes as claimed in claim 11, which is characterized in that wherein in step 2), the cellulose solvent is 1,8- bis-
11 carbon -7- alkene acrylates of azabicyclic [5.4.0], 11 carbon -7- alkene methoxyacetic acid of 1,8- diazabicylo [5.4.0]
Salt, 11 carbon -7- alkene ethoxyacetic acid salt of 1,8- diazabicylo [5.4.0], 11 carbon of 1,8- diazabicylo [5.4.0] -
At least one of 11 carbon -7- alkene glycollate of 7- alkene thioglycolic hydrochlorate or 1,8- diazabicylo [5.4.0]；When described
When cellulose solvent is two kinds of mixing, mixing quality ratio is 1:9~5:5.
14. purposes as claimed in claim 11, which is characterized in that in step 2), the quality hundred of the homogeneous cellulose solution
Dividing specific concentration is 2%~12%；The solution temperature of the cellulosic material is 60 DEG C~90 DEG C, magnetic agitation rotating speed 100rpm
~300rpm, the time that dissolution accounts for the cellulosic material of the cellulose solvent weight 5% is 10min to 150min.
15. purposes as claimed in claim 11, which is characterized in that in step 3), the coating thickness is 0.4mm~0.6mm,
The oven temperature is 70 DEG C~105 DEG C.
16. purposes as claimed in claim 11, which is characterized in that in step 4), the regenerated solvent is selected from deionized water, nothing
One of water-ethanol or acetone；The scavenging period of the regenerated solvent is 30min~45min.
17. purposes as claimed in claim 11, which is characterized in that in step 4), the regenerated solvent is deionized water.
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| CN114195791A (en) * | 2021-11-25 | 2022-03-18 | 华南理工大学 | Multi-element ionic liquid and preparation method and application thereof |
| CN114575040A (en) * | 2022-02-24 | 2022-06-03 | 北京林业大学 | Cellulose spray cloth and preparation method and application thereof |
| CN116102746A (en) * | 2023-02-20 | 2023-05-12 | 四川大学 | Method for dissolving cellulose based on proton type ionic liquid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113278166A (en) * | 2021-05-19 | 2021-08-20 | 青岛量子元基环保科技有限公司 | Dissolution regeneration and stable dispersion system of monomolecular cellulose |
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| CN116102746B (en) * | 2023-02-20 | 2024-04-12 | 四川大学 | Method for dissolving cellulose based on proton type ionic liquid |
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